Methined yestuffs



NLTED MET DYESTUFFS Oskar Riester, Dessau-Ziebigk, Germany, as-

signor, by mesne assignments, to General Ani-i 7 line & FilmCorporation, New York, N. 1 a corporation of Delaware No Drawing.Application October 28, 1938, Serial No. 237,474. In Germany November 8,1937 2' Claims. (CL 260-2510) 2, My present invention relates to newmethinedyestufi's. Dyestufl's are known which are produced bycondensation of aromatic bases containing nitro- 0H3 gen withbQdiesWhich contain a 5 is used for the condensation.

g b llii alreoverkthe coigdgnstatil lm mtay 1lice Niial'lgfgalgt yn esiso ri is Pa en 0. (R bemg hydrogen, alkyl or aryl) such as rhoy S damneor its N a1ky1 N ara1ky1 according to which a body of the generalformula or; N-arylj-substit-ution product. The parent ma- Y terlals forthe above mentioned process are obflky] tained for example bycondensation, ofjrhodanine y X withan w-aldehyde of the general formulaN alkyl f" is condensed with rhodanine. Dyestufiswithout CI-I-bridgesareobtained by the condensation of rhodanine with thiothiazolonium salts ortheir isomers of the general formula I alkyl wherein 81k 1 o-s- 1k 1n=l, 2' or 3, and O s y N a y l or Y-S, Se, CH-CH- or OH ITT X X alkylalkyl wherein X stands for an acid radicle (see British Patents Nos.423,792 and 438,420). (See. Brltlsh Patents NOS 438,278, 466,244 andother bases may alsg be used for the ynthesis ste d Of the aldehyde &ketone of of this intermediate dyestufi, for example a the generalformula dialkylaminobenzaldehyde which comes within the general formula"T a lkyi R1 *f Rz-I IQOHO I 0 v alkyl wherein. R1 andRz areakyl, and R2may join the (see British Patent No. 466,097) may be s d, benzenenucleus toforma ring. There may also There may further be used forcondensation be used aldehyde bases of the formula with the rhodanine,derivatives of the aldehydes 0 and ketones such as the oximes orphenylhydra- 4O zones, semicarbazides, thiosemicarbazides and N(GH=OH) Cthe like. 1 thsimilar rilyfestufis are obtained if a body having wherein71:5 1 2 or 3 and t nitrogenatpm may e: genera a be in a heterocyclicring.

All these dyestuffs can be condensed by the Y process of U. S.application Serial No. 233,205,

applied for by me on October l, 1938, andxen- C' (OH=OH) titled Basicmethine dyestuffs, now abandoned, H with alkyl-acid radicles, forexamplealkyl halides my} I or sulfates, to give dyestuffs more solublein wherein Waten 3, It is one object of my present invention to pro- Xstands for an acid radicle and vide a process of reacting further theaforemen- Y stands for S, 0, se, --CI-I=CII-- or v tioned dyestuffs whencondensed with alkfl- 3 4 radicles, and having an active thioalkyl groupwherein with quaternary salts of substitued or non-sub- R1 stands forthe same or various alkyls, stituted heterocyclic bases which have areactive R2 stands for H, alkyl, alkylene, aralkyl or aryl, CHa-group,in the presence of a condensing agent, R3 stands for H or the same orvarious alkyls for example pyridine or triethylamine in pro- 5containing up to 5 carbon atoms, panel at normal or raised temperatures,The R4, R5, R6 and R7 stands for H, H2 or the same thioalkyl groupsplits off, with formation of a or difierent alkyl, aralkyl or aryl andR4 and mercaptan, its place being taken by a methine R5 and R6 and R1respectively together form group derived from the reactive CHs-group.phenylene or a substitution product thereof or Another object of theinvention is the provil0" )3- or 813'-naphthylene,

sion of the new methine dyestuffs produced by Y and i h may be the sameor different, said process. Stand or O, S, Se,

Further objects will be apparent from the'following detaileddescription.

The reaction in the said process occurs as 15 cm w CH=CH, N-alkyl orN-aryl,

- R: oi=(on=o R5 ,.=o s Y f o1: (J-S-alkyl alkyl N R|\ R:/C1=(CH=CB5),,=C--S YCR4 alkyl N1 0 J--on=c -R; HS BX alkyl \N/ \III/ Il R7 In this equation X stands for halogen, alkyl sulfate, toluene sul-Y stands for O, S, Se, CH=CH- fonate, perchlorate or another desiredacid on, radicle, and 0 n=0, 1, 2 or 3. I

The new dyestuffs dye substantially more deeply than the correspondingrhodanine or or trimethine dyestufis from the same heterocyclic R standsfor alkyl' aryl, alkylene or aralkyl' bases, and give beautiful cleartones. While, for (1) R1stands for 'CH=CH instance, the Thiazole Purple(3.3'-dimethyl- CH3 4 benzthiazole trimethinecyanine iodide) is car- 0mine red, the dyestufl, which also contains rhodanine as a third ring,is actually blue. By the OH: new synthesis dyestuffs can be obtainedthroughand forms wi h R2 a heterocyclic ring n out the whole spectrum.Moreover, these dyech R2 is -CH2 2- for mstuffs are excellently suitedfor the optical sensistance, Example 1), tization of photographic silverhalide emulsions. n=0, 1, 2 or 3, or The invention is illustrated by thefollowing (2) R1 stands for H, examples:

R2 stands for arylene, which is in a ring with Example 1.The dyestuflobtained from thiathe alkyl group (see, for instance, Example zolinealdehyde and N-ethylrhodanine combined 14), with dimethyl sulfate: 11:0,1, 2 or 3, or (3) R1 stands for H, HCs

R2 stands for alkyl or aryl, there being a Hm benzene nucleus in1.4-position between CH=S0r the nitrogen atom N1 and the carbon C1, 00-s0Hi (see, for instance, Example 12), and MR2 CH3 \N/ may be in a ringwith the alkyl group (see, 5

i 5 3 Example gives, with 2-methyl-4.S-naphtholthiazole ethyl In allcases R3 and R4 stand for H Hz the same iodide f triethylamine inpmpanol red or a different alkyl, aralkyl or aryl and R3 and stuff havmgthe formula:

R4 together form a phenylene or a substitution product thereof ora-naphthylene, p-naphthylene or pp naphthylene, R5 stands for H oralkyl, and H2CS R1 stands for alkyl.

Dyestufls in class (1) have the following gen- H1 S eral formula JH /.L-

i U r 3 i i a-C\ o= CH-C n=os Y- s I I 00 I L Its absorption maximum is562 mu. R1 N \N/ Example 2.The dyestuff from eth'ylrhodanine 5 and1.1.3-trimethylindoline 2-methine-o-alde- R, B! 7 hyde combined withdiethyl sulfate gives, with Z-methyl-benzthiazole. ethyl iodide in.pyridine a to react with 2 -methyl-6H-naphtliooxazoleL ethyl violetdyestufi of the following constitution: iodide to give a red dyestuifi.

CH3 cm --o I 5 s C=OH-CH=C-S s e N I I I Y C=CH-H=C'S 0-- o C'OH= N/ CH3\N/ \1?' ([111 O(,\ /O'OH= a N N 62H C2115 I I Example 3.--The dyestufifrom rliodanine and 1.1.3-trimethyl-6-methoxyindoline-2-methine-waldehyde combined with dimethyl sulfate can be condensedwith z methyl-benzselenazole ethyl 1'5 iodide in isoquinoline to'a bluedyestufi:

Example 8.The dyestuff from -methy1-2- methothiobenzoxazole dimethylsulfate and a1-- lylrhodanine, having the formula Example -T condenationproduct from is condensed with dimethyl sulfate, and is furtherN-ethylbenzthlazojle-2-meth1ne-w-aldehyde and treated in pyridine with 1mol of 2.5 dimethy1 and dimethyl Sulfate is W benzoxazole. ethyl iodidefor half an hour at 90 react Wlth Q z Eb Y t C. The yellow dyestuffproduced has the followthiazolium bromide togive a greenish: blue dyemgformula;

stufi:

-0 C=OH'CH=C-S O 1 3 \N/ 0s 0 N I I. l C(L :--0H=J1 I O0 G'-CH=G V 2H5CH3 I OzHs N N N N C t I (IJ H v I H1 C2115 02115 2 a -I 40 CH Example5.The condensation product from II the intermediate product of6-diethyiamino-3- I ethylbenzthiazolediphenyl-formamidine and N- and itsabsorption maximum is 4'75 mu. allylrhodanine, combined With dimethylsulfate, Example 9.--The dyestuff from Z-methothiomay be furthercondensed with 2-methyl-6.7- benzthiazole ethyl sulfate andN-ethylrhodanine naphthothiazole ethyl iodide to give a blue-green iscondensed with dimethyl sulfate, and further dyestuff: treated inpyridine with 1 mol of 2-methyl-6.7-

( z s)zN O=CHCHC-S s C2115 PIT \N OH: (52115 t]; CH2

Emample dyestufi from N-ethylbenznaphtho-thiazole ethyl-para-toluene-sulfonate thiaZQIe-Z-methine-w-aldehyde and ethylrhodar ha f anhour at C. The orange-re dyenine, combined with dimethyl sulfate, iscaused stuff produ has the fOlloWing a! to react with le'pidine dimethylsulfate to give a green dyestufi:

and an absorption maximum of 510 mu. Example 7.The dyestuff fromN-methyl- Example 10.The dyestufi fromZ-methothiobenzthiazo1e-2-methine-w-a1dehyde and rhodabenzthiazole ethylsulfate and N-ethylrhodanine nine combined with dimethyl sulfate, iscaused 7 and dimethyl-sulfate is further treated with l 2,442,710 7 I 8mol of 2-methy1-4.5-dipheny1-oxazole diethyl sul- Z-methylbenzthlazoleethyl iodide. The bluefate. The deep yellow dyestufi produced has violetdyestufl has the following formula:

the following formula:

BBC-H c11=cs s ew w or am am Am: m f \N lzHs (1211s caH 43H Example 14.-The dyestuif from tetrahydroquinoline-N-propenal and N-allylrhodanineand dimethyl sulfate is further condensed with 2- l6 methyl-benzthiazoleethyl iodide in pyridine to a violet dyestufi having the followingconstitution:

and an absorption maximum of 580 m Example 11 .--The dyestufl fromN-ethyl-2-(yphenyliminopropene)-benzthiazole iodide (synthesized as inBritish Patent No. 412,309) and N- ethylrhodanine condensed with diethylsulfate iscaused to re- 0H1 act in pyridine with methylbenzthiazoleethyland an absorption maximum of 547 m para-toluene sulfonate at 70 C.for 2 hours and 3 Example mol of f is preclplta'ted p KI'solutloni Ablue dyestufi 2-benzthiazolino-butadienyl-) rhodanine (see having thepmdmed British Patent No. 450,953, Example 118) is l heated with /100mols of dimethylsulfate in an s oil bath to 115 for about 15 minutes,precipi- E tated by ethyl ether after cooling, dried and C=CHC=C--S Scondensed in pyridine (about /1oo mols) with \N/ I 1 /100 male of2.5.6-trimethy1benzoxazole ethyl-p- \N toluene sulfonate at 100 for onehour. The green dyestuff obtained is precipitated by an 01H: 01m 40aqueous potassium iodide solution and recrystallized from methanol; ithas the following Its absorption maximum is 596 m formula:

=CHCH=CH-GH=C-S o-- -03. \N/ I l! A: I-

1 0c '0H= 03H.

03H (J2EE Example 12.-The orange-yellow dyestuif from Example 16.Thedyestuff intermediate prodpara-dimethylaminobenzaldehyde and N-phenuctobtained as described in Example 15 and ylrhodanine is condensed withdiethyl sulfate having the formula and caused to react in pyridine with2-methyl- 5 6.7-naphthiazole ethyl iodide. The red-violet s dyestufiproduced has the following formula =CHCH=OHCH=C-S N orhsor- (132E oc/C'S.CH: B N

( laHl is condensed with 2-methyl-4-phenylthiazo1ediethylsulfate inpyridine at 105 for four hours L and precipitated as an iodide. Thegreen dye- CH: o--oH (CHmNQ =11 stufi produced has the followin formulao and an absorption maximum of 545 m 06H Example 13.-The dyestuif fromN-ethyl-2- methyl-indoline-5-aldehyde and ethylrhodanine Cam 2 anddimethyl sulfate is further condensed with The absorption maximum is at570 m 2,442,710 t. 9 10 I eieim: REFERENCES CITED 1. A process WhlChcomprises condensing N- A a ethylbenztmazole 2 m n methjne-. -a1dehydeThe following references are of record 1n the with N-ethylrhodanine anddimethyl sulfate, refile of this pat t: acting the condensation productthus produced 5 UNITED STATES PATENTS with4.5-dipheny1-2-tr1ethy1-N-ethy1thiazolil1m bromide in the presence of analkaline condens- Number Name Date ing agent BrOOker Sept. 11, 2. A dyehaving the following formula; 2,060,383 Schneider Nov. 10, 1936 102,148,441 Dawson Feb. 28, 1939 ---i 3 FOREIGN PA'I'EN'IS =CH OH:C SNumber Country Date N I Br- 466,097 Great Britain May 18, 1937 (32115 K15 466,244 Great Britain May 18, 1937 N N 0 lzHa J1me OSKAR RIESTER.

